1. Field of the Invention
The present invention relates to a processing composition for silver halide color photographic light-sensitive materials, more specifically, the present invention relates to a composition having an excellent function of reducing staining ascribable to residual sensitizing dyes in the processed light-sensitive material.
2. Description of the Related Art
With remarkable progress of digital camera and color printer, the processing of a silver halide color photographic light-sensitive material is demanded to quickly provide a high-quality image to users. However, since mere shortening of the processing time in conventional methods results in the completion of processing before sensitizing dyes in the light-sensitive material are thoroughly washed out, the highlight part or background part in the white portion of a color print is colored by a large amount of residual sensitizing dyes and the product cannot endure the viewing. In the case of a color negative film, the density in the minimum density part increases, whereby the color balance is lost and an appropriate print cannot be provided.
In recent years, use of silver halide tabular grains is an important basic technique in the preparation of a high-sensitivity light-sensitive material for photographing. This technique is advantageous in that since the amount of sensitizing dyes used per unit volume can be increased, the sensitivity and the sensitivity-graininess ratio are improved, but it has a problem that the amount of sensitizing dyes remaining in the processed light-sensitive material increases. Depending on the processing conditions, the increase in the amount of residual sensitizing dyes cannot be ignored and this causes a phenomenon such as lost of color balance due to increase in the density in the minimum density part of a color negative film or coloration of the highlight part of a color reversal film.
Research Disclosure, No. 20733 discloses a method of using a bistriazinylaminostilbene disulfonic acid compound as one example of the method for removing the residual color ascribable to sensitizing dyes. This method is widely used in the processing of color photographic light-sensitive materials. JP-A-6-329936 (the term xe2x80x9cJP-Axe2x80x9d as used herein means an xe2x80x9cunexamined published patent applicationxe2x80x9d) also discloses a bistriazinylaminostilbene disulfonic acid compound having excellent solubility and capable of reducing the residual color even in the processing shortened in the processing time.
Along with this quick processing of a photographic light-sensitive material, it is also demanded to reduce or maximally recycle the waste containers of processing agents or to more concentrate the processing compositions so as to reduce the cost for transportation or storage of the processing agents or processing chemicals. Accordingly, the additives used for the purpose of reducing the residual color must be suited for this concentration. However, a compound having an effect of reducing the residual color and capable of stably dissolving even in the state concentrated to a high salt concentration and satisfactorily providing the effect even in the processing reduced in the processing time has not yet been found out.
An object of the present invention is to solve the above-described problems in the techniques of the related art and provide a processing composition for silver halide color photographic light-sensitive materials, which can reduce the staining ascribable to the residual sensitizing dyes in the processed light-sensitive material and can be free of deposition of precipitates during the low-temperature storage of the processing composition.
The object of the present invention can be attained by the following inventions.
(1) A processing composition for silver halide photographic light-sensitive materials, comprising a compound represented by the following formula (I): 
wherein R11, R12, R13, R14, R21, R22, R23 and R24 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, L represents a phenylene group or a naphthylene group, and the pairs R11 and R12, R13 and R14, R21 and R22, and R23 and R24 each may be combined with each other to form a ring, provided that at least one group represented by xe2x80x94SO3K, xe2x80x94CO2M or xe2x80x94OH (wherein M represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium) is contained within the molecule, that the case where three or more of R11, R12, R13, R14, R21, R22, R23 and R24 R11, R12, R13, R14, R21, R22, R23 and R24 are an aryl group and the case where at least one of R11, R12, R13 and R14 and at least one of R21, R22, R23 and R24 are combined with each other to form a ring are excluded, and that a group represented by xe2x80x94Nxe2x95x90Nxe2x80x940 is not contained within the molecule
(2) An image formation method comprising using the processing composition for silver halide photographic light-sensitive materials described in (1).
(3) A compound represented by the following formula (I): 
wherein R11, R12, R13, R14, R21, R22, R23 and R24 each represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, L represents a phenylene group or a naphthylene group, and the pairs R11 and R12, R13 and R14, R21 and R22, and R23 and R24 each may be combined with each other to form a ring, provided that at least one group represented by xe2x80x94SO3M, xe2x80x94CO2M or xe2x80x94OH (wherein X represents a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or pyridinium) is contained within the molecule, that the case where three or more of R11, R12, R13, R14, R21, R22, R23 and R24 are an aryl group and the case where at least one of R11, R12, R13 and R14 and at least one of R21, R22, R23 and R24 are combined with each other to form a ring are excluded, and that a group represented by xe2x80x94Nxe2x95x90Nxe2x80x940 is not contained within the molecule.
The above-described compound of the present invention not only affords the means for attaining the object of the present invention but also has the following excellent properties. The compound of the present invention does not emit fluorescence and therefore, when used in combination with a bis(triazinylamino)stilbene disulfonic acid compound in the processing of a color print material, the fluorescent brightness and reduction in staining ascribable to sensitizing dyes can be independently controlled. Accordingly, the compound of the present invention can be preferably used in the processing of a color negative film or a color reversal film, where the processed light-sensitive material is not required to have fluorescent brightness. Furthermore, since the compound of the present invention is highly stable in the bleach-fixing composition or fixing composition as compared with the bis(triazinylamino)stilbene disulfonic acid compound and free of any deterioration in aging, so that stable processing performance can be maintained irrelevantly to the fluctuation in the processing amount per day or processing operation conditions.
The compound of formula (I) is described in detail below. The alkyl group represented by R11, R12, R13, R14, R21, R22, R23 and R24 is a substituted or unsubstituted alkyl group hating from 1 to 20, preferably from 1 to 8, more preferably from 1 to 4 carbon atoms and examples thereof include a methyl group, an ethyl group, an i-propyl group, an n-propyl group, an n-octyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 3-hydroxpropyl group, a 2-hydroxypropyl group, a 2-sulfoethyl group, a 2-methoxyethyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2-[2-(2-hydroxyethoxy)ethoxy]ethyl group, a 2-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)ethyl group, a 2,3-dihydroxypropyl group, a 3,4-dihydroxybutyl group and 2,3,4,5,6-pentahydroxyhexyl group.
The aryl group represented by R11, R12, R13, R14, R21, R22, R23 and R24 is a substituted or unsubstituted aryl group having from 6 to 20, preferably from 6 to 10, more preferably from 6 to 8 carbon atoms and examples thereof include a phenyl group, a naphthyl group, a 3-carboxyphenyl group, a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenyl group, a 2-sulfophenyl group and a 4-sulfophenyl group. The heterocyclic group represented by R11, R12, R13, R14, R21, R22, R23 and R24 is a monovalent group resulting from excluding one hydrogen atom from a substituted or unsubstituted 5- or 6-membered aromatic or nonaromatic heterocyclic compound having from 2 to 20, preferably from 2 to 10, more preferably from 3 to 8 carbon atoms and examples thereof include a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group and a 2-benzothiazolyl group.
R11, R12, R13, R14 R21, R22, R23 and R24 each is preferably a hydrogen atom, an alkyl group or an aryl group, more preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 2-sulfoethyl group, a 2-methoxyethyl group, 2-(2-hydroxyethoxy)ethyl group, a 2-[2-(2-hydroxyethoxy)ethoxy]ethyl group, a 2,3-dihydroxypropyl group, a 3,4-dihydroxybutyl group, a phenyl group, a 3-carboxyphenyl group, a 4-carboxyphenyl group, a 3,5-dicarboxyphenyl group, a 4-methoxyphenyl group, a 2-sulfophenyl group or a 4-sulfophenyl group, still more preferably a hydrogen atom, a methyl group, an ethyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2,3-dihydroxypropyl group, a phenyl group, a 3-carboxyphenyl group, a 4-carboxyphenyl group, a 2-sulfophenyl group or a 4-sulfophenyl group, particularly preferably a hydrogen atom, a methyl group, a sulfomethyl group, a 2-hydroxyethyl group, a 2-sulfoethyl group, a 2-(2-hydroxyethoxy)ethyl group, a 2,3-dihydroxypropyl group, a phenyl group or a 4-sulfophenyl group.
The phenylene group or naphthylene group represented by L is a substituted or unsubstituted phenylene or naphthylene group having from 6 to 20, preferably from 6 to 15, more preferably from 6 to 11 carbon atoms and examples thereof include 1,4-phenylene, 1,3-phenylene, 1,2phenylene, 1,5-naphthylene, 1,8-naphthylene, 4-carboxy-1,2-phenylene, 5-carboxy-1,3-phenylene, 3-sulfo-1,4-phenylene, 5-sulfo-1,3-phenylene, 2,5-dimethoxy-1,4-phenylene and 2,6-dichloro-1,4-phenylene.
L is preferably 1,4-phenylene, 1,3-phenylene, 1,2-phenylene, 1,5-naphthylene, 5-carboxy-1,3-phenylene or 5-sulfo-1,3-phenylene, more preferably 1,4-phenylene or 1,3-phenylene.
The ring formed by each pair R11 and R12, R13 and R14, R21 and R22, or R23 and R24 combined with each other is preferably a 5- or 6-membered ring. Examples of the ring include a pyrrolidine ring, a piperidine ring, a piperazine ring and a morpholine ring.
Among alkali metals and alkaline earth metals represented by M, preferred are Na and K. Examples of the ammonium group include an ammonium group, a triethylammonium group and a tetrabutylammoninm group. M is most preferably Na of K.
The compound of the present invention may contains at least one group represented by xe2x80x94SO3M, xe2x80x94CO2M or xe2x80x94OH in the molecule, at the terminal of R11, R12, R13, R14, R21, R22, R23 or R24, or on the phenylene or naphthylene group of L.
Specific examples of the compound of the present invention are set forth below, however, the present invention is not limited thereto. 
The compound represented by formula (I) can be synthesized by referring, for example, to Hirotsugu Matsui, Yuki Gosei Kagaku Kyokai Shi (Journal of Organic Synthetic Chemistry Association), Vol. 17, page 528 (1959) and Japanese Patent No. 2,618,748. More specifically, a method of reacting cyanuric chloride with a phenylenediamine derivative or a naphthalenediamine derivative and subsequently with an amine is preferred. A method of reacting the phenylenediamine derivative or naphthalenediamine derivative through two stages or at the final stage is also preferred. Examples of the solvent used for this reaction include water and organic solvents such as alcohols, ketones, ethers and amides. Among these, water and water-soluble organic solvents are preferred. A mixed solvent thereof may also be used and among the mixed solvents, a mixed solvent of water and acetone is most preferred. Examples of the base used include organic bases such as triethylamine, pyridine and 1,8-diazabicyclo[5,4,0]-7-undecene, and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate and potassium hydrogencarbonate. Among these, inorganic bases are preferred and in particular, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate are more preferred. The reaction temperature is from xe2x88x9220 to 150xc2x0 C., preferably from xe2x88x9210 to 100xc2x0 C. To speak more specifically, the reaction temperature is preferably xe2x88x9210 to 10xc2x0 C. at the first stage, from 0 to 40xc2x0 C. at the second stage and from 40 to 100xc2x0 C. at the third stage.
Compound (A-2) of the present invention was synthesized through the synthesis reaction route shown below. 
Synthesis of Compound 3
Into a three-neck flask, 37.6 g of Compound (1) and 280 ml of acetone were charged and while stirring in an ice-acetone bath, a solution containing 10.8 g of Compound (2) and 10 ml of acetone was added dropwise over 10 minutes while keeping the inner temperature at xe2x88x927 to 2xc2x0 C. After the completion of dropwise addition, a solution containing 10.6 g of sodium carbonate and 100 ml of water was added dropwise over 10 minutes. At this time, the inner temperature was from 2 to 7xc2x0 C. After the completion of dropwise addition, the ice-acetone bath was removed and stirring was continued for 30 minutes. The precipitated crystals were suction-filtered to obtain the objective Compound (3) as a crude product. This product was intactly used in the next step.
Synthesis of Compound 5
Into a three-neck flask, 25.0 g of Compound (4) and 250 ml of water were charged and while stirring, 21.2 g of sodium carbonate was added and dissolved. Subsequently, Compound (3) obtained above was added and the mixture was stirred at an inner temperature of 85xc2x0 C. for 5 hours. After the completion of stirring, the reaction solution was cooled to room temperature and the precipitated crystals were suction-filtered to obtain the objective Compound (5) as a crude product. This product was intactly used in the next step.
Synthesis of Compound A-2
Into a three-neck flask, Compound (5), 45.6 g of compound (5) and 200 ml of water were charged and the mixture was stirred at an inner temperature of 85xc2x0 C. for 10 hours. The reaction mixture was concentrated by a rotary evaporator and thereto, 500 ml of ethanol was added. The obtained crystals were suction-filtered to obtain 111.2 g of the objective Compound A-2. The purity of this compound was examined by liquid chromatography and found to be 64.5% (yield: 98%). The conditions for the liquid chromatography were as follows.
Column: TSK-gel ODS-80 TM (produced by Tosoh Corp.)
Eluent:
Solution A: obtained by adding 20 ml of PIC A reagent solution (produced by Waters) to 1 liter of water
Solution B: obtained by adding 20 ml of PIC A reagent solution (produced by Waters) to a mixed solution containing 800 ml of methanol and 200 ml of water.
Solution A/Solution B: changed in accordance with a gradient from 50/50 (0 min) to 0/100 (35 min)
Detection wavelength: 254 nm
The purity was determined by the peak area recorded on a chart under the above-described conditions.
Compound (A-3) of the present invention was synthesized through the synthesis reaction route shown below. 
Synthesis of Compound 9
Into a three-neck flask, 37.6 g of Compound (1) and 280 ml of acetone were charged and the mixture was stirred in an ice-acetone bath. Thereto, a solution containing 25.0 g of Compound (4), 21.2 g of sodium carbonate and 250 ml of water was added dropwise over 15 minutes at an inner temperature of xe2x88x927 to xe2x88x922xc2x0 C. After the completion of dropwise addition, the ice-acetone bath was removed and stirring was continued in an ice-cooling bath for 30 minutes. Thereto, a solution obtained by dissolving 10.8 g of Compound (8) in 100 ml of acetone was added dropwise over 10 minutes and subsequently, a solution obtained by dissolving 10.6 g of sodium carbonate in 30 ml of water was added dropwise over 5 minutes. Thereafter, the ice bath was removed and stirring was continued for 3 hours. The precipitated crystals were suction-filtered to obtain the objective Compound (9) as a crude product. This product was intactly used in the next step.
Synthesis of Compound A-3
Into a three-neck flask, Compound (9) obtained above, 45.6 g of Compound (6) and 200 ml of water were charged and after stirring at an inner temperature of 85xc2x0 C. for 5 hours, 150 ml of water was distilled off by a rotary evaporator. Thereto, 600 ml of methanol was added and the precipitated crystals were suction-filtered. After adding 50 ml of water, the crystals were dissolved under heating and thereto, 600 ml of methanol was added. The precipitated crystals were suction-filtered to obtain 89.0 g of the objective Compound A-3. The purity of this compound was examined by liquid chromatography and found to be 58.0% (yield: 71%). The conditions for the liquid chromatography were the same as those in Synthesis Example 1.
Compound (A-23) of the present invention was synthesized through the synthesis reaction route shown below. 
Synthesis of Compound 12
Into a three-neck flask, 37.6 g of Compound (1) and 280 ml of acetone were charged and the mixture was stirred in an ice-acetone bath. Thereto, a solution containing 21.0 g of Compound (10), 10.6 g of sodium carbonate and 250 ml of water was added dropwise over 15 minutes while keeping the inner temperature at xe2x88x927 to 0xc2x0 C. After the completion of dropwise addition, the ice-acetone bath was removed and stirring was continued in an ice-cooling bath for 30 minutes. Thereto, a solution obtained by dissolving 18.2 g of Compound (6) in 100 ml of acetone was added dropwise over 10 minutes and subsequently, a solution obtained by dissolving 10.6 g of sodium carbonate in 30 ml of water was added dropwise over 5 minutes. Thereafter, the ice bath was removed and stirring was continued for 3 hours. The precipitated crystals were suction-filtered to obtain the objective Compound (12) as a crude product. This product was intactly used in the next step.
Synthesis of Compound A-23
Into a three-neck flask, Compound (12) obtained above, 37.6 g of Compound (13) and 300 ml of water were charged and after stirring at an inner temperature of 85xc2x0 C. for 5 hours, 150 ml of water was distilled off by a rotary evaporator. Thereto, 600 ml of methanol was added and the precipitated crystals were suction-filtered. After adding 60 ml of water, the crystals were dissolved under heating and thereto, 600 ml of methanol was added. The precipitated crystals were suction-filtered to obtain 58.7 g of the objective Compound A-23. The purity of this compound was examined by liquid chromatography and found to be 72.0% (yield: 61%). The conditions for the liquid chromatography were the same as those in Synthesis Example 1.
In the case where the compound of the present invention has a plurality of asymmetric carbons, a plurality of stereoisomers is present for the same structure and the present invention includes all possible stereoisomers. Out of multiple stereoisomers, only one stereoisomer or a mixture of several stereoisomers may be used.
In the processing composition of the present invention, one compound represented by formula (I) may be used or a plurality of the compounds may be used in combination. The number of compounds and the kind of the processing composition into which the compound is incorporated may be freely selected. The compound of the present invention may also be used in combination with one or a plurality of bis(triazinylarino)stilbene disulfonic acid compounds). Also at this time, the number of compounds used and the kind of the processing solution into which the compound is incorporated may be freely selected.
The bis(triazinylamino)stilbene disulfonic acid compound used in combination with the compound of the present invention may be a known or commercially available diaminostilbene-base fluorescent brightening agent. Preferred examples of known bis(triazinylamino)stilbene disulfonic acid compounds include the compounds described in JP-A-6-329936, JP-A-7-140625 and JP-A-10-104809. Commercially available compounds are described, for example, in Senshoku Note (Dyeing Note), 19th ed., pp. 165-168, Sensyoku Sha. Among the products described therein, Blankophor BSUliq. REU and Hakkol BRK are preferred.
The compound of the present invention may be used in combination with a compound having a triazine ring other than bis (triazinylamino)stilbene disulfonic acid compounds in order to further improve solubility or residual color reduction effect. The compound having a triazine ring to be used in combination may be used singly or in combination. Examples of the compound having a triazine ring are set forth below, however, the present invention is not limited thereto. 
The processing composition for use in the present invention is described in detail below. The processing composition for use in the present invention means a processing composition necessary for the processing in performing the image information of a silver halide color photographic light-sensitive material. Specific examples thereof include a color developing composition, a bleaching composition, a bleach-fixing composition, a fixing composition, a water washing composition and a stabilizing composition. The processing solution may also be a black-and-white developing composition, a reversal composition or a pre-bleaching composition. These processing compositions may be prepared as a tank solution or a replenisher and may be prepared to have a concentration on use or as a concentrated solution. In the case of a concentrated solution, the processing composition of the present invention is mixed with water on use at a predetermined ratio and used as a replenisher or a tank solution. The compound of the present invention is characterized in that the composition formed in the state of a solution has excellent precipitation stability, however, the compound of the present invention may also be used for a processing solution in the granular, tablet, powder or slurry form.
The composition of the present invention may also be an additive composition. The term xe2x80x9cadditive compositionxe2x80x9d as used herein means a composition which is added to a tank solution or a replenisher necessary for the processing in performing the image formation of a silver halide color photographic light-sensitive material before or during the processing and exerts a function of controlling the photographic performance.
In the processing composition of the present invention, the concentration of the compound of formula (I) is, in the case of a working solution, from 0.05 to 20 mmol/L, preferably from 0.15 to 15 mmol/L, more preferably from 0.2 to 10 mmol/L. In the case where the processing composition of the present invention is diluted with water or another processing composition and then used, the concentration in the processing composition is a value obtained by multiplying the concentration magnification by the concentration in a solution on use. The xe2x80x9cconcentration magnificationxe2x80x9d used herein means, as commonly used in the art, a ratio between the component concentration in the processing composition and the component concentration in the processing solution on use.
The concentration of the bis(triazinylamino)stilbene disulfonic acid compound may be, in the case of a working solution, from 0.05 to 20 mmol/L, preferably from 0.1 to 10 mmol/L, more preferably 0.2 to 10 =mmol/L. In the case where the processing composition of the present invention is diluted with water or another processing composition and then used, the concentration in the processing composition is a value obtained by multiplying the concentration magnification by the concentration in a solution on use.
The concentration of the compound having a triazine ring other than the bis(triazinylamino)stilbene disulfonic acid compound may be, in the case of a working solution, from 0.01 to 10 mmol/L, preferably from 0.05 to 5 mmol/L, more preferably 0.1 to 5 mmol/L. In the case where the processing composition of the present invention is diluted with water or another processing composition and then used, the concentration in the processing composition is a value obtained by multiplying the concentration magnification by the concentration in a solution on use.
In the image formation method of the present invention, at least one processing step uses the processing composition of the present invention. The present invention may be used in a plurality of steps or all steps.
The process for producing the processing composition of the present invention includes several methods but good results may be obtained by the following three processes. In the practice of the present invention, the production process is, however, not limited to these three processes.
Process A
A process of previously introducing a small amount of water into a mixing tank and sequentially charging constituent chemicals thereinto while stirring.
Process B
A process of previously mixing constituent chemicals in a mixing tank and charging a small amount of water en bloc.
Process C
A process of previously classifying the constituent chemicals into appropriate groups, dissolving each group in water or a hydrophilic organic solvent to form a concentrated solution and mixing respective concentrated solutions.
A production process partially employing these processes may also be used.
The processing composition of the present invention may be a developing composition, a bleach-fixing composition, a fixing composition, a water washing or stabilizing composition or an additive composition and these processing compositions are described below one by one.
The color developing composition of the present invention contains a color developing agent and the color developing agent is preferably a known aromatic primary amine color developing agent, more preferably a p-phenylenediamine derivative. Typical examples thereof are set forth below, however, the present invention is not limited thereto. Recently, in some black-and-white light-sensitive materials, a coupler is added to form a black color and a black-and-white image is formed using a general purpose color developing solution. The processing composition of the present invention can also be applied to such light-sensitive materials.
1) N,N-Diethyl-p-phenylenediamine
2) 4-Amino-N,N-diethyl-3-methylaniline
3) 4-Amino-N-(xcex2-hydroxyethyl) N-methylaniline
4) 4-Amino-N-ethyl-N-(xcex2-hydroxyethyl)aniline
5) 4-Amino-3-methyl-N-ethyl-N-(xcex2-hydroxyethyl)aniline
6) 4-Amino-3-methyl-N-ethyl-N-(3-hydroxypropyl)aniline
7) 4-Amino-3-methyl-N-ethyl-N-(4-hydroxybutyl)aniline
8) 4-Amino-3-methyl-N-ethyl-N-(xcex2-methanesulfonamidoethyl)aniline
9) 4-Amino-N,N-diethyl-3-(xcex2-hydroxyethyl)aniline
10) 4-Amino-3-methyl-N-ethyl-N-(xcex2-methoxyethyl)aniline
11) 4-Amino-3-methyl-N-(xcex2-ethoxyethyl)-N-ethylaniline
12) 4-Amino-3-methyl-N-(3-carbamoylpropyl)-N-n-propylaniline
13) 4-Amino-3-methyl-N-(4-carbarmoylbutyl)-N-n-propylaniline
14) N-(4-Amino-3-methylphenyl)-3-hydroxypyrrolidine
15) N-(4-Amino-3-methylphenyl)-3-hydroxymethylpyrrolidine
16) N-(4-Amino-3-methylphenyl)-3-pyrrolidinecarboxamide
Among these p-phenylenediamine derivatives, Compounds 5) to 8) and 12) are preferred, and Compounds 5) and 8) are more preferred. These p-phenylenediamine derivatives in the state of a solid are usually a sulfate, a hydrochloride, a p-toluenesulfonate, a naphthalenedisulfonate or an N,N-bis(sulfonatoethyl)hydroxylamine. These derivatives may also be added as a free form having no counter salt. The concentration of the aromatic primary amine developing agent is from 4 to 100 mmol/L, preferably from 6 to 50 mmol/L, more preferably from 8 to 25 mmol/L, in the solution on use.
The color developer of the present invention may contain a compound capable of preventing the precipitation of color developing agent and examples thereof include polyethylene glycols, arylsulfonic acids, alkylsulfonic acids and urea compounds described in JP-A-11-174643. Among these, diethylene glycol, polyethylene glycol 300, p-toluenesulfonic acid and salts thereof, a linear alkylsulfonic acid having from 5 to 9 carbon atoms and salts thereof, and ethylene urea are preferred, because these scarcely affect the photographic properties and exhibit good effect.
The color developing composition of the present invention preferably contains a compound capable of preventing the color developing agent from deterioration due to air oxidation, namely, a preservative. Sulfite and hydroxylamine are preferred as the inorganic preservative. Such an inorganic preservative exhibits an extremely high preservation activity and is preferably used in combination with an organic preservative. Depending on the light-sensitive material to be processed, sulfite and hydroxylamine sometimes adversely affect the photographic properties during the process of color development and therefore, in some cases, only either one is used or these are not substantially contained but only an organic preservative is used.
Examples of effective organic preservatives include hydroxyamine derivatives, hydroxamic acids, hydrazides, phenols, xcex1-hydroxyketones, xcex1-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxyl radicals, alcohols, oximes, diamides, condensed cyclic amines, cyclic amides, salicylic acids, polyethyleneimines, alkanolamines and aromatic polyhydroxy compounds. Among these organic preservatives, hydroxylamine derivatives described in JP-A-3-56456 and JP-A-3-33845, and compounds described in JP-A-3-33846 and JP-A-6-148841 are preferred.
The hydroxylamine derivative is preferably used in combination with an alkanolamine from the standpoint of improving the stability of color developer in the continuous processing. Examples of the compound with which the hydroxylamine is preferably used in combination include triisopropanolamine and triethanolamine. A combination use with a cyclic amide compound is also preferred and among the cyclic amide compounds, xcex5-caprolactam is particularly preferred.
The pH of the color developing composition of the present invention is preferably from 9.5 to 13.5 and the color developer prepared therefrom is from 9.0 to 12.2, preferably from 9.9 to 11.2. In order to maintain the pH, a buffer is preferably added and the buffer is preferably a potassium or sodium salt of an inorganic salt such as carbonate, bicarbonate, phosphate, borate and tetraborate. Also, an organic compound such as 5-sulfosalicylic acid, xcex2-alanine, proline and trishydroxyaminomethane is preferably used, however, the present invention is not limited to these compounds. The buffer is incorporated to a concentration of 0.1 mol/L or more, preferably from 0.1 to 0.4 mol, in terms of a concentration of color developing replenisher.
The color developing composition of the present invention may contain various chelating agents as a precipitation inhibitor, such as calcium and magnesium. The chelating agents may be used individually or in combination of two or more. Preferred compounds therefor include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,Nxe2x80x2,Nxe2x80x2-tetramethylenesulfonic acid, ethylenediaminesuccinic acid (s,s form), 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-dihosphonic acid and 1,2-dihydroxybenzen-4,6-disulfonic acid. The chelating agent may be sufficient if it is added in an amount large enough to conceal metal ion in the color developer. The chelating agent is usually added to a concentration of approximately from 0.1 to 10 g/L.
If desired, an arbitrary development accelerator may be added to the color developing composition of the present invention. Examples of the development accelerator include polyalkylene oxide, 1-phenyl-3-pyrazolidones, alcohols and carboxylic acids.
In addition, an arbitrary antifoggant may be added to the color developing composition of the present invention. Examples of the antifoggant include metal halides such as potassium bromide and potassium iodide, and organic antifoggants represented by a nitrogen-containing heterocyclic compound. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolidine and adenine. Other than these, an alkylcarboxylic acid, an arylcarboxylic acid or a saccharide may also be added, if desired.
In the color development applied to the present invention, the processing temperature is, in the case of a color print light-sensitive material, from 30 to 55xc2x0 C., preferably from 35 to 50xc2x0 C., more preferably from 38 to 45xc2x0 C. The developing time is from 5 to 90 seconds, preferably from 6 to 60 seconds, more preferably from 10 to 45 seconds. The replenishing amount, which is preferably smaller, is suitably from 15 to 200 mL, preferably from 20 to 120 mL, more preferably from 30 to 60 mL, per 1 m2 of the light-sensitive material.
In the case of a color negative film, the processing temperature is from 30 to 55xc2x0 C., preferably from 35 to 50xc2x0 C., more preferably from 38 to 45xc2x0 C. The developing time is from 45 seconds to 5 minutes, preferably from 60 seconds to 4 minutes, more preferably from 90 seconds to 3 minutes to 15 seconds. The replenishing amount, which is preferably smaller, is suitably from 10 to 200 mL, preferably from 12 to 60 mL, more preferably from 15 to 30 mL, per 1 roll of 24 exp.
In the case of a color reversal film, the processing temperature is from 32 to 45xc2x0 C., preferably from 35 to 40xc2x0 C., more preferably 36.5 to 39.5xc2x0 C. The developing time is from 4 to 8 minutes, preferably from 5 to 7 minutes more preferably from 5 minutes 30 seconds to 6 minutes 30 seconds. The replenishing amount, which is preferably smaller, is suitably from 1,000 to 3,000 mL, preferably from 1,500 to 2,800 mL, more preferably from 2,000 to 2,400 mL, per 1 m2 of the light-sensitive material.
The color developing composition obtained by concentrating the replenisher described in JP-A-11-174643, JP-A-11-194461 and JP-A-11-194462 is a preferred embodiment.
The bleaching agent for use in the bleaching composition and the bleach-fixing composition of the present invention may be a known bleaching agent but in particular, an organic complex salt (a complex salt of, for example, an aminopolycarboxylic acid or an organic acid such as citric acid, tartaric acid and malic acid), a persulfate and a hydrogenperoxide of iron(III) are preferred. Two or more bleaching agents may also be used in combination.
Among these, an organic complex salt of iron(III) is preferred in view of rapid processability and environmental antipollution. Examples of the aiminopolycarboxylic acid or a salt thereof useful for forming an organic complex salt of iron(III) include compounds such as biodegradable ethylenediaminesuccinic acid (ss-form), biodegradable N-2-carboxylatoethyl)-L-aspartic acid, biodegradable xcex2-alaninediacetic acid, biodegradable methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid and glycol ether diaminetetraacetic acid. These compounds may be in the form of a sodium salt, a potassium salt, a lithium salt or an ammonium salt. Among these compounds, ethylenediaminesuccinic acid (s,s-form), N-(2-carboxylatoethyl)-L-aspartic acid, xcex2-alaninediacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid and 1,3-propylenediaminetetraacetic acid are preferred because their iron(III) complex salts provide good photographic properties. The ferric complex salt may be used in the complex salt form or a ferric ion complex salt may be formed from a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ammonium ferric nitrate and ferric phosphate, using a chelating agent such as aminopolycarboxylic acid. The chelating agent may also be used in excess of the amount necessary for the formation of a ferric ion complex salt. The concentration of the bleaching agent in the bleaching or bleach-fixing solution is, in terms of a concentration in a solution on use, from 0.01 to 1.0 mol/L, preferably from 0.05 to 0.50 mol/L, more preferably from 0.1 to 0.5 mol/L.
A buffer is also preferably added to the bleaching or bleach-fixing solution. The buffer selected varies depending on the intended pH, however, preferred examples of the compound therefor include organic acids such as succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, sulfosuccinic acid and acetic acid, organic bases such as imidazole and dimethylimidazole, and the compounds represented by formulae (A-a) and (B-b) of JP-A-9-211819. The amount of this compound added is preferably from 0.005 to 3.0 mol/L, more preferably from 0.05 to 1.5 mol/L, in a solution on use. The pH region of the bleaching solution is preferably from 2 to 7, more preferably from 3 to 6. In the case of the bleach-fixing solution, the pH is preferably from 3 to 8, more preferably from 4 to 7.
In the bleach-fixing of a color print light-sensitive material applied to the present invention, the processing temperature is from 30 to 55xc2x0 C., preferably from 35 to 50xc2x0 C., more preferably from 38 to 45xc2x0 C. The bleach-fixing time is from 5 to 90 seconds, preferably from 8 to 60 seconds, more preferably from 10 to 45 seconds. The replenishing amount, which is preferably smaller, is suitably from 20 to 200 mL, preferably from 25 to 120 mL, more preferably from 30 to 50 mL, per 1 m2 of the light-sensitive material.
In the bleaching of a color negative film, the processing temperature is from 30 to 55xc2x0 C., preferably from 35 to 50xc2x0 C., more preferably from 38 to 45xc2x0 C. The bleaching time is from 12 seconds to 2 minutes, preferably from 15 seconds to 1 minute and 15 seconds, more preferably from 18 to 60 seconds. The replenishing amount, which is preferably smaller, is suitably from 2.5 to 50 mL, preferably from 3 to 25 mL, more preferably from 4 to 12 mL, per 1 roll of 24 exp.
In the bleaching of a color reversal film, the processing temperature is from 30 to 45xc2x0 C., preferably from 33 to 40xc2x0 C., more preferably from 37 to 39xc2x0 C. The bleaching time is from 4 to 8 minutes, preferably from 5 to 7 minutes, more preferably from 5 minutes and 30 seconds to 6 minutes and 30 seconds. The replenishing amount, which is preferably smaller, is suitably from 160 to 400 mL, preferably from 180 to 300 mL, more preferably from 200 to 250 mL, per 1 m2 of the light-sensitive material.
The fixing agent for use in the bleach-fixing composition and the fixing composition of the present invention is a known fixing agent. Specific examples thereof include thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylenebisglycolic acid, 3,6-dithia-1,8-octanediol and thioether compounds described in JP-A-4-317055; thioureas; and water-soluble silver halide dissolving agents described in JP-A-4-143757 and JP-A-4-230749, such as mesoionic compound. These may be used individually or in combination of two or more thereof. The fixing agent is preferably a thiosulfate, more preferably ammonium thiosulfate. The concentration of the fixing gent in the fixing solution or bleach-fixing solution is preferably from 0.3 to 2 mol/L, more preferably from 0.5 to 1.5 mol/L.
The bleach-fixing composition or the fixing composition preferably contains a buffer. Preferred examples of the buffer include heterocyclic organic bases such as imidazole and dimethylimidazole, aminoalkylenesulfonic acid such as taurine, and dibasic acids such as succinic acid, maleic acid and malonic acid. The pH is preferably from 3 to 8, more preferably from 4 to 7.
The bleach-fixing composition and the fixing composition of the present invention preferably contain, as a preservative, a compound capable of releasing sulfite ion, namely, a sulfite, a bisulfite or a metabisulfite. This compound is preferably added in the form of a potassium salt, a sodium salt or an ammonium salt. Also, an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid, is preferably contained. Such a compound is preferably contained to a concentration of 0.02 to 1.0 mol/L in a solution on use. Other than those described above, an ascorbic acid, a carbonyl bisulfite adduct or a carbonyl compound may be added as the preservative.
The bleach-fixing composition and the fixing composition of the present invention may also contain a mercapto nitrogen-containing heterocyclic compound capable of forming stable silver ion so as to improve the image preservability, such as mercaptotriazole, aminomercaptotriazole and N-methylmercaptoimidazole, or a bisamidine, a bisguanidine or a monoamidine described in JP-A-5-303185, which accelerates the washing out of developing agent. Other than these, a polymer such as polyethylene glycol or polyvinylpyrrolidone, a chelating agent, a defoaming agent, an antifungal and the like may be added, if desired, to the bleaching composition and the fixing composition of the present invention.
In the bleach-fixing of a color print light-sensitive material applied to the present invention, the processing temperature, the bleach-fixing time and the replenishing amount are the same as those described above. In the fixing of a color negative film, the processing temperature is from 30 to 55xc2x0 C., preferably from 35 to 50xc2x0 C., more preferably from 38 to 45xc2x0 C. The bleaching time is from 20 seconds to 2 minutes, preferably from 30 seconds to 1 minute and 40 seconds, more preferably from 35 seconds to 1 minute and 20 seconds. The replenishing amount, which is preferably smaller, is suitably from 4 to 60 mL, preferably from 5 to 40 mL, more preferably from 6 to 30 mL, per 1 roll of 24 exp.
In the fixing of a color reversal film, the processing temperature is from 30 to 45xc2x0 C., preferably from 33 to 40xc2x0 C., more preferably from 37 to 39xc2x0 C. The fixing time is from 2 to 6 minutes, preferably from 3 to 5 minutes, more preferably from 3 minutes and 30 seconds to 4 minutes and 30 seconds. The replenishing amount, which is preferably smaller, is suitably from 800 to 2,000 mL, preferably from 900 to 1,500 mL, more preferably from 1,000 to 1,250 mL.
The washing composition and the stabilizing composition of the present invention may contain formalin, formaldehyde, pyruvinaldehyde, a formaldehyde bisulfite adduct described in U.S. Pat. No. 4,921,779, or an N-methylol compound described in JP-A-5-34889, so as to inhibit discoloration of a dye and generation of staining, which are ascribable to the residual magenta coupler. Also, washing composition and the stabilizing composition of the present invention preferably contain an arylsulfinic acid such as p-toluenesulfinic acid, m-carboxybenzenesulfinic acid and p-aminobenzenesulfinic acid. Furthermore, a surfactant as a water-cutting agent, a chelating agent as a hard water-softening agent, a buffer for adjusting the pH, a defoaming agent, an antifungal, an antiseptic and the like may be added, if desired.
The pH is preferably from 4 to 10, more preferably from 5 to 8. The processing temperature may be variously selected according to the use and properties of the light-sensitive material, however, the processing temperature is generally from 20 to 50xc2x0 C., preferably from 25 to 45xc2x0 C.
The additive composition of the present invention preferably comprises the compound of the present invention and water, however, if desired, a water-soluble aliphatic compound, a bis(triazinylamino)stilbene disulfonic acid compound, a chelating agent, an inorganic salt and the like may be added. The water-soluble aliphatic compound is preferably a glycol such as diethylene glycol and polyethylene glycol 300 (average molecular weight; 300), or an alkanolamine such as triethanolamine and triisopropanolamine. In particular, diethylene glycol is preferred. The additive composition of the present invention can be added to any processing bath or replenisher which is considered necessary for the processing in performing the image formation of a silver halide color photographic light-sensitive material. In the additive composition, the compound of the present invention is preferably concentrated and the concentration ratio to the working solution is from 50 to 4,000 magnifications, preferably from 100 to 2,000 magnifications, more preferably from 200 to 1,000 magnifications. One preferred embodiment is a method of adding the additive composition of the present invention to a fixing bath and/or a fixing replenisher in the color reversal processing, however, the present invention is not limited thereto.
Out of the photographic element which is processed using the present invention, the light-sensitive material may contain any normal silver halide such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and a mixture thereof. In one embodiment, the light-sensitive material of the photographic element is a high silver chloride light-sensitive material containing at least 50 mol % or more of silver chloride, preferably at least 90 mol % or more of silver chloride, and in many cases, this is used as a light-sensitive material for color print.
In another embodiment, at least one emulsion in the light-sensitive material mainly comprises silver bromide (at least 50 mol % of silver bromide). The photographic element most preferably has one or more color recording layer and each color recording layer comprises one or more silver halide emulsion, mainly silver bromide emulsion, as used in color negative film or color reversal film. The photographic element containing a light-sensitive material processed by practicing the present invention may be a nmonochromatic element or a multicolor element. The photographic element may also have a magnetic recording layer known in this technical field.
Individual photographic elements are described in detail, for example, in Research Disclosure (hereinafter simply referred to as xe2x80x9cRDxe2x80x9d), specifically, in RD 17643, pp. 23-27, RD18716, pp. 647-650, RD307105, pp. 866-868 and 873-879, and RD36544, pp. 501-541. These are related to useful (negative or positive) silver halide emulsions and preparation methods thereof, various sensitizers, dye-forming coupler, image dye stabilizer, dye, ultraviolet absorbent, filter, binder, hardening agent, plasticizer, lubricant, coating aid, surfactant, antistatic agent, matting agent, paper or film support, and various image formation methods of a negative or positive image-forming color element.
It is advantageous to construct the processing composition of the present invention in a form such that all components for the solution on use are contained in one composition, namely, a one-part structure. However, if it is not preferred to allow the constituent components to come into contact for a long period of time in the color developing composition, bleach-fixing composition or the like, the constituent components may be separated into two or more liquid agents or solid admixtures and the processing composition may be constructed to have a two-part or three-part structure. These processing agent structures are usually called a one-, two- or three-part structure according to the naming of International Standard IS05989 (Terms of Mixed Processing Agents). The effects and characteristic features of the invention are not lost even when the processing composition of the present invention is divided into parts. Among these structures, a one-part structure is particularly preferred for the color developing composition.
For the container of the processing composition of the present invention, a known material may be used. The container may be formed of a single material or a composite material, for example, a composite material comprising a material having high gas permeability and a material having high stability against alkali. In view of re-use or recycling, the container is preferably composed by a single construction material. Examples of the material used for the container include polyester resin, polyolefin resin, acrylic resin, ABS resin, epoxy resin, polyamide resin such as nylon, polyurethane resin, polystyrene resin, polycarbonate resin, PVA, polyvinyl chloride, polyvinylidene chloride and polyethylene resin. Among these, a container composed of a single material using a polyester resin such as polyethylene terephthalate and polyethylene naphthalate, or a polyolefin resin such as polyethylene and polypropylene, is preferred. In particular, the container material is more preferably a polyethylene resin and still more preferably a high-density polyethylene resin (HDPE).
Insofar as the processing composition is not affected, the container material for use in the present invention may contain carbon black, titanium white, a pigment, calcium carbonate, a plasticizer having compatibility with the material, and the like. The container material is preferably such that polyethylene occupies 85% or more in the material and a plasticizer is not contained, more preferably such that polyethylene occupies 95% or more and a plasticizer is not contained.
The shape and structure of the container into which the processing composition of the present invention is filled can be freely designed according to the purpose. In addition to a fixed form bottle, a freely shrinkable type described in JP-A-1-235950, a container with a flexible partition described in JP-A-62-134626, and the like may also be used. The container described in JP-A-11-282148 is particularly preferred as the container for the processing composition of the present invention in view of the capacity, space efficiency, self-sustained standing, shape retentivity and re-use/recycling property. A preferred embodiment is a kit where a plurality of compositions of the present invention are filled in containers having the same shape and shame volume and formed of a single constituent material and these containers are integrated into a single cartridge. Examples thereof include the cartridge described in JP-A-2000-3014. The combination of processing compositions in the cartridge can be freely selected. The cartridges described in JP-A-11-295858 and JP-A-11-288068, where a developing composition, a bleaching composition and a fixing composition are integrated, are a preferred embodiment.
The present invention is described in greater detail below by referring to the Examples, including the stability of the processing composition of the present invention against the deposition of precipitates and also the photographic properties. However, the present invention should not be construed as being limited thereto.